Process for the production of broken down lignin-cellulose silicate copolymers

ABSTRACT

Small particles of cellulose-containing plants and an oxidated silicon compound are mixed with an alkali metal hydroxide then heated to 150° to 220° C. while agitating thereby producing an alkali metal broken down lignin-cellulose silicate polymer which is then reacted with a polysubstituted organic compound to produce a broken down lignin-cellulose silicate copolymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of my copending U.S. patentapplication, Ser. No. 112,290, filed Jan. 15, 1980, which is acontinuation-in-part of my U.S. patent application, Ser. No. 029,202,filed Apr. 12, 1979, now U.S. Pat. No. 4,220,757.

BACKGROUND OF THE INVENTION

This invention relates to a process for the production of broken downlignin-cellulose silicate copolymers utilizing an alkali metal brokendown lignin-cellulose silicate polymer and a polysubstituted organiccompound in an aqueous solution which are reacted to produce a brokendown cellulose copolymer which may be in the form of a precipitate or asan aqueous dispersion.

The products produced by this invention have many commercial uses andmay be utilized as molding powder, as coating agents for wood and metal,as films, as fillers, as impregnating agents, as adhesives, as binders,as caulking material, as fibers, as sheets, as casting materials, asputty material and may be further reacted with organic compounds toproduce useful resinous products and foams.

A broken down cellulose silicate copolymer is obtained by reacting thefollowing components:

Component (a) broken down alkali metal lignin cellulose-silicatepolymer;

Component (b) an organic compound having at least two carbon atoms, eachof which is attached to a substituent which will split off during thereaction;

Component (c) optionally, a solvent;

Component (d) optionally, an emulsifying or dispersion agent;

Component (a)

Component (a), a broken down alkali metal lignin cellulose silicateproduct, is produced by the processes outlined in my U.S. patentapplication, Ser. No. 029,202, filed Apr. 12, 1979, and is incorporatedinto this invention.

Broken down, alkali metal lignin-cellulose polymers are produced bymixing 3 parts by weight of a cellulose-containing plant or plantderivative, 1 to 2 parts by weight of an oxidated silicon compound and 2to 3 parts by weight of an alkali metal hydroxide, then heating themixture at 150° C. to 220° C. while agitating for 5 to 60 minutes.

Any suitable plant or the products of plants which contain cellulose maybe used in this invention. The plant material is preferred to be in theform of small dry particles such as sawdust. Suitable plants include,but are not limited to trees, bushes, agricultural plants, weeds, vines,straw, flowers, kelp, algae and mixtures thereof. Wood is the preferredplant. Commercial and agricultural waste products may be used, such asstalks, paper, cotton clothes, bagasses, etc. Wood fibers (wood pulp)with lignin removed may be used in this invention. Plants that have beenpartially decomposed, such as humus, peat, certain soft brown coal,manure containing cellulose, etc., may also be used in this invention.

Any suitable alkali metal hydroxide may be used in this invention.Suitable alkali metal hydroxides include sodium hydroxide, potassiumhydroxide and mixtures thereof. Sodium hydroxide is the preferred alkalimetal hydroxide.

Any suitable oxidated silicon compound may be used in this invention.Suitable oxidated silicon compounds include silica, e.g., hydratedsilica, hydrated silica containing Si-H bonds (silicoformic acid),silicia sol, silicic acid, silica, etc., alkali metal silicates, e.g.,sodium silicates, potassium silicate, lithium silicate, etc., naturalsilicates with free silicic acid groups and mixtures thereof.

The broken down alkali metal lignin-cellulose silicate polymer is darkbrown to black in color, has at least one --COH radical removed fromeach cellulose molecule, the usual lignin-cellulose bond is not brokenin most of the cases and the cellulose molecules are broken down intosmaller molecules of alkali metal broken down cellulose silicate andcarbohydrates which are water soluble. When a cellulose polymer such ascotton or wood with the lignin removed is reacted with an alkali metalhydroxide by the process of this invention a black water soluble brokendown alkali metal lignin-cellulose silicate polymer is produced; thispolymer may be reacted with a mineral acid until the pH is about 6 and ablack, foamed broken down lignin-cellulose silicate resinous product andcarbohydrates are produced. The foam is produced by the release of CO₂which was removed from the cellulose polymer.

Compound (b)

Any suitable organic compound that will react with the broken downalkali metal lignin-cellulose silicate polymer may be used. As organiccompound is preferred, having at least two carbon atoms, of which one isattached to a substituent, which are split off during the reaction.These organic compounds which are the reactants used in the preparationof broken down cellulose silicate copolymers have the graphical skeletoncarbon structure of

    X--C--C--X

where

    --C--C--

represents two adjacent carbon atoms, or

    X--C--R--CX

where X and X represent the substituents which splet off during thereaction. The R between the pair of reactive carbon atoms is selectedfrom the following groups: saturated straight chain carbon atoms,unsaturated carbon atoms, ether linkages, aromatic structures, andothers, for it is to be understood that other intervening structures maybe employed. The X and X substituents can be halogen, acid sulfate,nitrate, acid phosphate, bicarbonate, formate, acetate, propionate,laurate, oleate, stearate, oxalate, acid malonate, acid tartrate, acidcitrate and others. Examples of these organic compounds include, but arenot limited to: ##STR1## and others such as methylene chloride orbromide, ethylene dichloride, ethylene dibromide, propylene dichlorideor dibromide, halohydrins, epihalohydrins, dihalides of unsaturatedhydrocarbon gases derived from pressure-cracking processes, naturalgas-cracking processes as well as compounds having more than twosubstituents such as 1,1,2 trichloroethane; 1,2,4 trichlorobutane;1,2,3,4 tetrachlorobutane; trichloromesitylene and the like. Mixtures ofthese compounds may be used in this process.

Component (c)

Any suitable inorganic or organic solvent may be used in this invention.Suitable solvents include but not limited to water, alcohols, such asmethyl alcohol, ethyl alcohol, isopropyl alcohol, propyl alcohol,polyhydroxy organic compounds (polyols) such as ethylene glycol,propylene-1,2 and -1,3-glycol, butylene-1,4- and -2,3-glycol,hexane-1,6-diol, 2-methyl-propane-1,3-diol, glycerol, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylol ethane,pentaerythritol, diethylene glycol, triethylene glycol, tetraethyleneglycol, polyethylene glycol, dipropylene glycol, polypropylene glycol,dilintylene glycol, polybutylene glycols; polyesters, polyethers,sucrose polyethers and sucrose amine polyethers with at least 2,generally from 2 to 8 hydroxyl groups per molecule; and mixturesthereof.

Component (d)

Emulsifying or dispersing agents may be used in this invention, anysalt-stable compound which is highly hydrophobous in nature and has ahydrophobic group as one component and a hydrophilic group as the othermay be used. The emulsifying or dispersing agent which may be used forthe formation of lattices of small-particle size are those compoundshaving such groups as SO₃, SO₄, NH₂, etc., as the hydrophilic componentand a higher molecular weight alkyl, aralkyl, aryl or alkyl group as thehydrophobic component. The more hydrophobic the entire compound becomes,the smaller the polymer particle size becomes in the latex.

Compounds which are most suitable as emulsifying or dispersing agentsfor latex formation are the lignin sulfonates such as calcium and sodiumlignin sulfonates, alkyl benzene sulfonates having more than 20 carbonatoms in the alkyl group, aryl alkyl sulfonates, sorbitan monolaurates,especially those which are oil soluble and slightly water soluble, andothers. The dominance of the hydrophobic group over the hydrophilicgroups is one of the important factors in producing a latex ofsmall-particle size. The molecular weight of the hydrophobic group aloneis not the deciding factor, for aryl groups, for example, may be morehydrophobic than an alkyl group of like molecular weight. Aryl alkylgroups are more hydrophobic than alkyl aryl groups of the same molecularweight. Thus by selection of emulsifying or dispersing agents, theparticle size of the latex can be varied to suit any particular needs.Emulsifiers which can be used are sorbitan monolaurates, alkyl arylsulfonates, alkyl aryl sulfates, aryl alkyl sulfonates, aryl alkylsulfates, lignin sulfonates, methyl cellulose, sulfonated petroleumfractions, polymerized alkyl aryl sulfonates, polymerized aryl alkylsulfonates, soybean lecithin, and the like. The particle size can becontrolled by selecting emulsifying or dispersing agents havingdifferent molecular-weight hydrophobic groups as well as differenthydrophobic groups. The particle size will also vary with theconcentration of the emulsifying or dispersing agents.

In certain cases, other dispersing agents such as magesium hydroxide oraqueous dispersions of peptized starch, gelatin, glue, blood-albumen,egg albumen, or the like, may be used.

The primary object of this invention is to produce broken downlignin-cellulose silicate copolymers. Another object is to producebroken down lignin-cellulose silicate copolymer that may be used asmolding powder, as coating agents for wood and metal, as films, asfilters, as impregnating agents, as adhesives, etc. Another object is toproduce broken down lignin-cellulose silicate copolymers which willreact with polyisocyanates to produce foam which may be utilized asthermal and sound insulation. Still another object is to producepolysulfide broken down lignin-cellulose silicate copolymers. Stillanother object is to produce polysulfide-silicate-broken down cellulosesilicate copolymers. Still another object is to produce aldehyde-brokendown lignin-cellulose silicate copolymers.

DETAILED DESCRIPTION OF THE INVENTION

The preferred process to produce a broken down lignin-cellulosecopolymer is to slowly add a substituted organic compound having atleast two carbon atoms, each of which is attached to a substituent whichwill split off during the reaction, to a broken down metallignin-cellulose silicate polymer in the amount wherein the mols of thesubstituted radicals are about equal to the mols of the alkali radicalsin the mixture, while agitating for about 30 minutes; at a temperaturebelow the boiling temperature of the reactants; the reaction is completein about 30 minutes to 8 hours thereby producing a broken downlignin-cellulose silicate copolymer. The salt produced may be removed bywashing with water and then filtering.

In an alternate method the broken down alkali metal lignin-cellulosesilicate copolymer is added to a solvent such as water, alcohols,polyhydroxy alcohols and mixtures thereof to produce a solutioncontaining 10% to 70% broken down alkali metal lignin-cellulose silicatepolymer, then a substituted organic compound having at least two carbonatoms, each of which is attached to a substituent which will split offduring the reaction, is slowly added to said solution while agitating,at a temperature between ambient and just below the boiling temperatureof the reactants for about 30 minutes; the reaction is complete in 30minutes to 8 hours. When water is used as the solvent an emulsifying ordispersing agent may be used in the amount of 1% to 5% to assist inmixing the broken down alkali metal lignin-cellulose silicate polymerand the substituted organic compound. The broken down lignin-cellulosesilicate copolymer may be recovered by filtration from an aqueoussolution.

The chemical reaction of this invention may take place in any suitablephysical condition. Ambient pressure is usually satisfactory, but incertain conditions, an elevated or below ambient pressure may be useful.In cases when halogenated organic compounds are used the reaction isspeeded up by increased temperature (up to 200° C.) and pressure (up to1,500 psi). When organic dihydrogen sulfate compounds are used it may benecessary to decrease the temperature by cooling the reactants. Ambienttemperature is usually satisfactory. A suitable water solublepolysulfide such as an alkali metal polysulfide, alkaline earth metalpolysulfide, ammonium polysulfide, polysulfides of ethanolamine andmixtures thereof, in an aqueous solution may be mixed with the brokendown alkali metal lignin-cellulose silicate polymer in the ratio of 1 to20 parts by weight of the water soluble polysulfide to 10 parts byweight of the broken down alkali metal lignin-cellulose polymer then asubstituted organic compound, having at least two carbon atoms, each ofwhich is attached to a substituent which will split off during thereaction, is slowly added while agitating between ambient temperatureand the boiling temperature of the reactants for about 30 minutes. Thereaction is complete in 30 minutes to 8 hours thereby producing apolysulfide-broken down lignin-cellulose silicate condensation product.The condensation product settles out and the water and salt are removedby decantation or by filteration.

The polysulfide-broken down lignin-cellulose silicate condensationproduct may be utilized as a molding resin and molded into usefulobjects by heat (110° to 180°) and pressure. It may be utilized as acaulking compound, as a curing agent for epoxy resins and may be reactedchemically with polyisocyanates and isocyanate-terminated polyurethaneprepolymers to produce useful resinous products and foams; the foams maybe used for thermal and sound insulation.

A suitable water soluble polysulfide silicate such as an alkali metalpolysulfide silicate in an aqueous solution may be mixed with the brokendown alkali metal lignin-cellulose silicate polymer in the ratio of 1 to20 parts by weight of the water soluble polysulfide to 10 parts byweight of the broken down alkali metal lignin-cellulose silicate polymerthen a substituted organic compound, having at least two carbon atoms,each of which is attached to a substituent which will split off duringthe reaction, is slowly added while agitating between ambienttemperature and the boiling temperature of the reactants for about 30minutes. The reaction is complete in 30 minutes to 8 hours, therebyproducing a polysulfide-broken down lignin-cellulose-silicatecondensation product. The condensation product settles out and the waterand salt are removed by decantation or by filteration.

The alkali metal polysulfide silicate compound may be produced by any ofthe methods as outlined in U.S. patent application Ser. No. 19,178 filedon Mar. 9, 1979, by David H. Blount, M.D. In the production of thealkali metal polysulfide silicate compound sulfur in any of its commonlyknown forms may be used; the sulfur may also be reacted with an alkalimetal compound to produce alkali metal polysulfides. In the productionof alkali metal polysulfide silicate compounds any suitable alkali metalhydroxide may be used; sodium hydroxide is the preferred alkali metalhydroxide. Any suitable oxidated silicon compound may be used such assilica, e.g. hydrated silica, silicon dioxide, silicoformic acid,polysilicoformic acid, silicic acid gel and silica sol, alkali metalsilicates and natural silicates with free silicic acid radicals andmixtures thereof, may be used to produce alkali metal polysulfidesilicate.

The alkali metal polysulfide silicate compound is produced by mixing 2parts by weight of an alkali metal hydroxide, 1 to 4 parts by weight ofa sulfur and 1 to 2 parts by weight of an oxidated silicon compound thenheating the mixture to just above the melting temperature of sulfurwhile agitating for 10 to 30 minutes thereby producing an alkali metalpolysulfide silicate compound.

The polysulfide-broken down lignin-cellulose silicate condensationproduce may be utilized as a molding powder and molded into usefulobjects such as art objects, gaskets, knobs, handles, gears, etc., byheat (120° to 200°) and pressure. The condensation product may also beused with polyepoxy resins as a curing agent by heating the mixture tothe softening temperature of the polysulfide-broken downlignin-cellulose-silicate condensation product. When about equal partsby weight of the broken down alkali cellulose polymer and water solublepolysulfide is utilized in the production of the polysulfide-broken downlignin-cellulose-silicate condensation product it may be utilized as acaulking agent and may also be cured by vulcanizing using heat, pressureand a metal oxide such as zinc oxide powder. The polysulfide-broken downcellulose-silicate condensation product in the form of a powder may befurther reacted with a polyisocyanate or isocyanate-terminatedpolyurethane prepolymer to produce a polyurethane silicate foam; whichmay be utilized for thermal and sound insulation.

Any suitable aldehyde compound may be reacted with the broken downalkali metal lignin-cellulose silicate polymer before reacting thebroken down alkali metal cellulose polymer with a substituted organiccompound. Suitable aldehydes include but not limited to formaldehyde,acetaldehyde, propionic aldehyde, furfural, crotonaldehyde, acrolein,butyl aldehyde, paraformaldehyde pentanals, hexanals, petanals andmixtures thereof in the ratio of 1 to 5 parts by weight of the aldehydeto 2 parts by weight of the broken down alkali metal lignin-cellulosesilicate polymer. The aldehyde is mixed with the water soluble brokendown alkali metal lignin-cellulose silicate polymer then agitated at atemperature between ambient temperature and the boiling temperature ofthe aldehyde and at ambient pressure for 10 to 120 minutes therebyproducing an aldehyde alkali metal lignin-cellulose silicate copolymer.The aldehyde-alkali metal-lignin-cellulose silicate copolymer is thenmixed with a substituted organic compound having at least two carbonatoms, each which is attached to a substituent which will split offduring the reaction, to said aldehyde-alkali metal-lignin-cellulosesilicate copolymer in the amount wherein the mols of the substitutedradicals are about equal to the mols of the alkali radicals in themixture, then heated to a temperature between ambient temperature andthe boiling temperature of the reactants while agitating at an ambientpressure to 1,500 psi for about 30 minutes; the reaction is complete in30 minutes to 8 hours thereby producing a broken down cellulosecopolymer. The copolymer gradually settles out and may be recovered bydecantation of filtration.

The broken down lignin-cellulose silicate copolymer utilizing analdehyde may be ground into a molding powder then molded into usefulobjects such as knobs, panels, art objects, handles, etc., by heat(180°-220° C.) and pressure. The broken down lignin-cellulose cellulosecopolymer may be further reacted with polyisocyanates to produce usefulsolid objects or foams which may be used as thermal and soundinsulation, for packaging, construction panels, etc. The broken downcellulose copolymer is also soluble in many of the common solvents andmay be used as protective coating for wood and metal and as an adhesive.

The broken down lignin-cellulose silicate copolymers resinous productswill react chemically with suitable polyisocyanates and/orpolyisothiocyanates to produce resinous products and foams.

Any suitable organic polyisocyanate may be used according to theinvention, including aliphatic, cycloaliphatic, araliphatic, aromaticand heterocyclic polyisocyanates and mixtures thereof. Suitablepolyisocyanates which may be employed in the process of the inventionare exemplified by the organic diisocyanates which are compounds of thegeneral formula:

    O═C═N--R--N═C═O

wherein R is a divalent organic radical such as an alkylene, aralkyleneor arylene radical. Such suitable radicals may contain, for example, 2to 20 carbon atoms. Examples of such diisocyanates are:

tolylene diisocyanate,

p,p'-diphenylmethane diisocyanate,

phenylene diisocyanate,

m-xylylene diisocyanate,

chlorophenylene diisocyanate,

benzidene diisocyanate,

naphthylene diisocyanate,

decamethylene diisocyanate,

hexamethylene diisocyanate,

pentamethylene diisocyanate,

tetramethylene diisocyanate,

thiodipropyl diisocyanate,

propylene diisocyanate,

ethylene diisocyanate.

Other polyisocyanates, polyisothiocyanates and their derivatives may beequally employed. Fatty diisocyanates are also suitable and have thegeneral formula: ##STR2## where x+y totals 6 to 22 and z is 0 to 2,e.g., isocyanastearyl isocyanate.

It is generally preferred to use commercially readily availablepolyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and anymixtures of these isomers ("TDI"), polyphenyl-polymethylene-isocyanatesobtained by anilineformaldehyde condensation followed by phosgenation("crude MDI"), and modified polyisocyanate containing carbodiimidegroups, allophanate groups, isocyanurate groups, urea groups, imidegroups, amide groups or bioret groups, said modified polyisocyanatesprepared by modifying organic polyisocyanates thermally or catalyticallyby air, water, urethanes, alcohols, amides, amines, carboxylic acids, orcarboxylic acid anhydrides, phosgenation products of condensates oraniline or anilines alkyl-substituted on the nucleus, with aldehydes orketones may be used in this invention. Solutions of distillationresidues accumulating during the production of tolylene diisocyanates,diphenyl methane diisocyanate, or hexamethylene diisocyanate, inmonomeric polyisocyanates or in organic solvents or mixtures thereof maybe used in this invention. Organic triisocyanates such astriphenylmethane triisocyanate may be used in this invention.Cycloaliphatic polyisocyanates, e.g., cyclohexylene-1,2-, cyclohexylene1,4-; and methylene-bis-(cyclohexyl-4,4') diisocyanate may be used inthis invention. Suitable polyisocyanates which may be used according tothe invention are described, e.g., by W. Siefkin in Justus LiebigsAnnalen der Cherie, 562, pages 75 to 136. Inorganic polyisocyanates arealso suitable according to the invention.

Organic polyhydroxyl compounds (polyols) may be used in this inventionwith polyisocyanates or may be first reacted with a polyisocyanate toproduce isocyanate-terminated polyurethane prepolymers and then alsoused in this invention.

Reaction products of from 50 to 99 mols of aromatic diisocyanates withfrom 1 to 50 mols of conventional organic compounds with a molecularweight of, generally, from about 200 to about 10,000 which contain atleast two hydrogen atoms capable of reacting with isocyanates, may alsobe used. While compounds which contain amino groups, thiol groups,carboxyl groups or silicate groups may be used, it is preferred to useorganic polyhydroxyl compounds, in particular, compounds which containfrom 2 to 8 hydroxyl groups, especially those with a molecular weight offrom about 800 to about 10,000 and preferably from about 1,000 to about6,000, e.g., polyesters, polyethers, polythioethers, polyacetals,polycarbonates or polyester amides containing at least 2, generally from2 to 8, but preferably dihydric alcohols, with the optional addition oftrihydric alcohols, and polybasic, preferably dibasic, carboxylic acids.Instead of the free polycarboxylic acids, the correspondingpolycarboxylic acid anhydrides or corresponding polycarboxylic acidesters of lower alcohols or their mixtures may be used for preparing thepolyesters. The polycarboxylic acid may be aliphatic, cycloaliphatic,aromatic and/or heterocyclic and may be substituted, e.g., with halogenatoms and may be unsaturated; examples include: succinic acid, adipicacid, sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalicacid anhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, endomethylene tetrahydrophthalic acid anhydride,glutaric acid anhydride, fumaric acid, maleic acid, maleic acidanhydride, dimeric and trimeric fatty acid such as oleic acid,optionally mixed with monomeric fatty acids, dimethylterephthalate andbis-glycol terephthalate. Any suitable polyhydric alcohol may be usedsuch as, for example, ethylene glycol; propylene-1,2- and -1,3-glycol;butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol;neopentyl glycol;cyclohexanedimethanol-(1,4-bis-hydroxymethylcyclohexane);2-methylpropane-1,3-diol; glycerol; trimethylol propane; hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane; pentaerythritol;quinitol, mannitol and sorbitol; methylglycoside, diethylene glycol;triethylene glycol; tetra ethylene glycol; polyethylene glycols;dipropylene glycol; polypropylene glycols; dibutylene glycol andpolybutylene glycols. The polyesters may also contain a proportion ofcarboxyl end groups. Polyesters of lactones, such as c-caprolactone, orhydroxycarboxylic acid such as ω-hydroxycaproic acid, may also be used.

The polyethers with at least 2, generally from 2 to 8 and preferably 2or 3, hydroxyl groups used according to the invention are known and maybe prepared, e.g., by the polymerization of epoxides, e.g., ethyleneoxide propylene oxide, butylene oxide, tetrahydrofurane oxide, styreneoxide or epichlorohydrin, each with itself, e.g., in the presence ofBF₃, or by addition of these epoxides, optionally as mixtures orsuccessively, to starting components which contain reactive hydrogenatoms such as alcohols or amines, e.g., water, ethylene glycol;propylene-1,3- or -1,2-glycol; trimethylol propane;4,4-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine orethylenediamine; sucrose polyethers such as those described, e.g., inGerman Auslegeschriften Nos. 1,176,358 and 1,064,938, may also be usedaccording to the invention. It is frequently preferred to use polyetherswhich contain predominantly primarily OH groups (up to 90% by weight,based on the total OH groups contained in the polyether). Polyethersmodified with vinyl polymers such as those which may be obtained bypolymerizing styrene or acrylonitrites in the presence of polyethers,(U.S. Pat. Nos. 3,383,3510 3,304,273; 3,523,093 and 3,110,695; andGerman Pat. No. 1,152,536) and polybutadienes which contain OH groupsare also suitable.

By "polythioethers" are meant, in particular, the condensation productsof thiodiglycol with itself and/or with other glycols, dicarboxylicacids, formaldehyde, aminocarboxylic acids or amino alcohols. Theproducts obtained are polythio-mixed ethers or polythioether esteramides, depending on the cocomponent.

The polyacetals used may be, for example, the compounds which may beobtained from glycols, 4,4'-dihydroxydiphenylmethylmethane, hexanediol,and formaldehyde. Polyacetals suitable for the invention may also beprepared by the polymerization of cyclic acetals.

The polycarbonates with hydroxyl groups used may be of the kind, e.g.,which may be prepared by reaction diols, e.g., propane-1,3-diol;butane-1,4-diol; and/or hexane-1,6-diol or diethylene glycol,triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g.,diphenylcarbonates or phosgene.

The polyester amides and polyamides include, e.g., the predominantlylinear condensates obtained from polyvalent saturated and unsaturatedcarboxylic acids of their anhydrides, any polyvalent saturated andunsaturated amino alcohols, diamines, polyamines and mixtures thereof.

Polyhydroxl compounds which contain urethane or urea groups, modified orunmodified natural polyols, e.g., castor oil, carbohydrates andstarches, may also be used. Additional products of alkylene oxides withphenol formaldehyde resins or with ureaformaldehyde resins are suitablefor the purpose of the invention.

Organic hydroxl silicate compound as produced in U.S. Pat. No. 4,139,549may also be used in this invention.

Examples of these compounds which are to be used according to theinvention have been described in High Polymers, Volume XVI,"Polyurethanes, Chemistry and Technology", published by Saunders-FrischInterscience Publishers, New York, London, Volume I, 1962, pages 32 to42 and pages 44 to 54, and Volume II, 1964, pages 5 to 16 and pages 198and 199; and in Kunststoff-Handbuck, Volume VII, Vieweg-Hochtlen,Carl-Hanser-Verlag, Munich, 1966, on pages 45 to 71.

If the polyisocyanates or the prepolymer which contains NCO groups havea viscosity above 2000 cP at 25° C., it may be advantageous to reducethe viscosity thereof by mixing it with a low-viscosity organicpolyisocyanate and/or an inert blowing agent or solvent.

Inorganic polyisocyanates and isocyanate-terminated polyurethanesilicate prepolymers may also be used in this invention.

Polyisocyanate curing agents and/or polyisocyanate activators(catalysts) may be used in the process of producing polyurethaneresinous or foamed products. The following are examples ofpolyisocyanate curing agents and activators:

1. Water.

2. Water containing 10% to 70% by weight of an alkali metal silicate,such as sodium and/or potassium silicate. Crude commercial alkali metalsilicate may contain other substances, e.g., calcium silicate, magnesiumsilicate, borates or aluminates and may also be used. The molar ratio ofthe alkali metal oxide to SiO₂ is not critical and may vary within theusual limits, but is preferably between 4 to 1 and 0.2 to 1.

3. Water containing 20% to 50% by weight of ammonium silicate.

4. Water containing 5% to 40% by weight of magnesium oxide in the formof a colloidal dispersion.

5. Alkali metal metasilicate such as sodium metasilicate, potassiummetasilicate and commercial dry granular sodium and potassium silicates.Heating is required to start the curing reaction.

6. Water containings 20% to 70% by weight of silica sol.

7. Activators (catalysts) which act as curing agents and are added tothe polyurethane silicate prepolymer in the amount of 0.001% to 10% byweight. They may be added in water.

(a) Tertiary amines, e.g., triethylamine; tributylamine;N-methylmorpholine,; N-ethylmorpholine; N,N,N',N'-tetramethylenediamine;1,4-diazobicyclo-(2,2,2)-octane; N-methyl-N'-dimethylaminoethylpiperazine; N,N-dimethylbenzylamine; bis(N,N-diethylaminoethyl)adipate;N,N-diethylbenzylamine; pentamethyldiethylenetriamine;N,N-dimethylcyclohexylamine; N,N,N',N'-tetramethyl-1,3-butaneediamine;N,N-dimethyl-beta-phenylethylamine; and 1,2-dimethylimidazole. Suitabletertiary amine activators which contain hydrogen atoms which arereactive with isocyanate groups include, e.g., triethanolamine;triisopanolamine; N,N-dimethylethanolamine; N-methyldiethanolamine;N-ethyldiethanolamine; and their reactive products with alkylene oxides,e.g., propylene oxide and/or ethylene oxide and mixtures thereof.

(b) Organo-metallic compounds, preferably organo-tin compounds such astin salts of carboxylic acid, e.g., tin acetate, tin octoate, tin ethylhexoate, and tin laurate and the dialkyl tin salts of carboxylic acids,e.g., dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleateor diocyl tin diacetate.

(c) Silaamines with carbon-silicon bonds are described, e.g., in BritishPat. No. 1,090,589, may also be used as activators, e.g.,2,2,4-trimethyl-1,2-silamorpholine or1,3-diethylaminoethyl-tetramethyldisiloxane.

(d) Other examples of catalysts which may be used according to theinvention and details of their action are described inKunstoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 96 and 102.

8. Water containing 1% to 10% by weight of bases which contain nitrogensuch as tetraalkyl ammonium hydroxide.

9. Water containing 1% to 10% by weight of alkali metal hydroxides suchas sodium hydroxide; alkali metal phenolates such as sodium phenolate oralkali metal alcoholates such as sodium methylate.

10. Water containing sodium polysulfide in the amount of 1% to 10% byweight.

11. Water containing 20% to 70% by weight of a water-binding agent,being capable of absorbing water to form a solid or a gel, such ashydraulic cement, synthetic anhydrite, gypsum or burnt lime.

12. Mixtures of the above-named curing agents.

Surface-active additives (emulsifiers and foam stabilizers) may also beused according to the invention. Suitable emulsifiers are, e.g., thesodium salts of ricinoleic sulphonates or of fatty acid, or salts offatty acids with amines, e.g., oleic acid diethylamine or stearic aciddiethanolamine. Other surface-active additives are alkali metal orammonium salts of sulphonic acids, e.g., dodecylbenzine sulphonic acidor dinaphthyl methane disulphonic acid; or of fatty acids, e.g.,ricinoleic acid, or of polymeric fatty acids.

The foam stabilizers used are mainly water-soluble polyester siloxanes.These compounds generally have a polydimethylsiloxane group attached toa copolymer of ethylene oxide and propylene oxide. Foam stabilizers ofthis kind have been described, e.g., in U.S. Pat. No. 3,629,308. Theseadditives are preferably used in quantities of 0% to 20%, but preferably0.01% to 20%, by weight, based on the reaction mixture.

Negative catalysts, for example, substances which are acidic inreaction, e.g., hydrochloric acid or organic acid halides, known cellregulators, e.g., paraffins, fatty alcohols or dimethyl polysiloxanes,pigments or dyes, known flame-retarding agents, e.g.,tris-chloroethylphosphate or ammonium phosphate and polyphosphates,stabilizers against aging and weathering plasticizers, fungicidal andbacteriocidal substances and fillers, e.g., barium sulphate, kieselguhr,carbon black or whiting, may also be used according to the invention.

Further examples of surface additives, foam stabilizers, cellregulators, negative catalysts, stabilizers, flame-retarding substances,plasticizers, dyes, fillers and fungicidal and bacteriocidal substancesand details about methods of using these additives and their action maybe found in Kunststoff-Handbuch, Volume VI, produced by Vieweg andHochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 103 to 113.The halogenated paraffins and inorganic salts of phosphoric acid are thepreferred fire-retarding agents.

The preferred curing agent is an aqueous solution of silicates, sodiumsilicate, and/or potassium silicate in water which is normally known aswater glass. Aqueous solutions of silicates may be prepared in the formof 25% to 70% silicates. Silica sols which may have an alkaline or acidpH may also be used; they should have solid contents of 15% to 50%.Silica sols are generally used in combination with aqueous silicatesolutions. The choice of concentration depends mainly on the desired endproduct. Compact materials or materials with closed cells are preferablyproduced with concentrated silicated solutions, which, if necessary, areadjusted to a lower viscosity by addition of alkali metal hydroxide.Solutions with concentrations of 40% to 70% by weight can be prepared inthis way. On the other hand, to produce open-celled, light-weight foams,it is preferred to use silicate solutions with concentrations of 20% to45% by weight in order to obtain low viscosities, sufficiently longreaction times and low unit weights. Silicate solutions withconcentrations of 15% to 45% are also preferred when substantialquantities of finely divided inorganic fillers are used.

Suitable flame-resistant compounds may be used in the products of thisinvention such as those which contain halogen or phosphorus, e.g.,tributylphosphate; tris(2,3-dichloropropyl)-phosphate;polyoxypropylenechloromethylphosphonate; cresyldiphenylphosphate;tricresylphosphate; tris-(beta-chloroethyl)-phosphate;tris-(2,3-dichloropropyl)-phosphate; triphenylphosphate; ammoniumphosphate; perchloroinated diphenyl phosphate; perchlorinated terephenylphosphate; hexabromocyclodecane; tribromophenol; dibromopropyldiene,hexabromobenzen; octabromodiphenylether; pentabromotoluol;poly-tribromostyrol; tris-(bromocresyl)-phosphate; tetrabromobis-phenolA; tetrabromophthalic acid anhydride; octabromodiphenyl phosphate;tris-(dibromopropyl)-phosphate; calcium hydrogen phosphate; sodium orpotassium dihydrogen phosphate; disodium or dipotassium hydrogenphosphate; ammonium chloride; phosphoric acid; polyvinylchloridetetomers chloroparaffins as well as further phosphorus- and/orhalogen-containing flame-resistant compounds as they are described inKunststoff-Handbuch, Volume VII, Munich, 1966, pages 110 and 111, whichare incorporated herein by reference. The organic halogen-containingcomponents are, however, preferred in the polyurethane products.

The ratios of the essential reactants and optional reactants which leadto the polyurethane silicate resinous or foamed product of thisinvention may vary, broadly speaking, with ranges as follows:

(a) 1 to 95 parts by weight of broken down lignin-cellulose silicatecopolymer;

(b) 50 parts by weight of polyisocyanate, polyisocyanate orisocyanate-terminated polyurethane prepolymer;

(c) up to 20% by weight of a foam stabilizer;

(d) up to 50% by weight of a chemically inert blowing agent; boilingwithin the range of from -25° C. to 80° C.;

(e) up to 10% by weight of an activator;

(f) up to 200 parts by weight of a water-binding agent

(g) 1 to 95 parts by weight of a polyol.

Percentages are based on the weight of the reactants, resinous productpolyol and polyisocyanate.

In the cases where the viscosity of the polyisocyanate is too high, itmay be reduced by adding a low-viscosity isocyanate, or even by addinginert solvents such as acetone, diethyl ether of diethylene glycol,ethyl acetate and the like.

In cases where the curing agent contains an aqueous alkali silicate, itis preferred that the isocyanate-terminated polyurethane prepolymer besulphonated. It is usually sufficient to react the isocyanate-terminatedpolyurethane prepolymer with concentrated sulphuric acid or oleum ofsulfur trioxide in order to produce a sulphonated poly(urethanesilicate) prepolymer containing the sulphonic group in the amount of3-100 milli-equivalents/100 g. The reaction will take place bythoroughly mixing the sulphuric acid or oleum or sulfur trioxide withthe isocyanate-terminated polyurethane prepolymer at ambient temperatureand pressure. In some cases where sulfur trioxide is used, an increasedpressure is advantageous. The polyisocyanate may be modified to containionic groups before reacting with the polyester-silicate resinousproducts.

The sulphonated isocyanate-terminated polyurethane prepolymer can bedirectly mixed with an aqueous silicate solution, in which case thecorresponding metal salt is formed in situ. The sulphonatedpoly(urethane silicate) prepolymer may be completely or partlyneutralized at the onset by the addition of amines, metal alcoholates,metal oxides, metal hydroxide or metal carbonates.

Water-binding components may be used in this invention, includingorganic or inorganic water-binding substances which have, first, theability to chemically combine, preferably irreversibly, with water and,second, the ability to reinforce the poly(urethane silicate) plastics ofthe invention. The term "water-binding component" is used herein toidentify a material, preferably granular or particulate, which issufficiently anhydrous to be capable of absorbing water to form a solidor gel such as mortar of hydraulic cement.

A water-binding component such as hydraulic cement, syntheticanhydrides, gypsum or burnt lime may be added to any of the componentsto produce a tough, somewhat flexible solid or cellular solid concrete.The water-binding component may be added in amounts from 0-200% byweight, based on the weight of the reactants. When a water-binding agentis added and when the curing agent is an aqueous alkali metal silicatesolution, a halogen or phosphorus-containing compound or mixture thereofmay be added in the amount of 1% to 30% by weight, based on the weightof the reactants.

Suitable hydraulic cements are, in particular, Portland cement,quick-setting cement, blast-furnace Portland cement, mild-burnt cement,sulphate-resistant cement, brick cement, natural cement, lime cement,gypsum cement, pozzolan cement and calcium sulphate cement. In general,any mixture of fine ground lime, alumina and silica that will set to ahard product by admixture of water, which combines chemically with theother ingredients to form a hydrate, may be used. There are many kindsof cement which can be used in the production of the compositions of theinvention and they are so well known that a detailed description ofcement will not be given here; however, one can find such a detaileddescription in Encyclopedia of Chemical Technology, Volume 4, SecondEdition, Published by Kirk-Othmer, pages 684-710, of the type of cementwhich may be used in the production of this invention and areincorporated herein by reference.

Organic blowing agents may be used to improve or increase the foaming toproduce cellular solid plastics such as acetone, ethyl acetate,methanol, ethanol, halogenated alkanes, e.g., methylene chloride,chloroform, ethylidene chloride, vinylidene chloride,monofluorotrichloromethane, chlorodifluoromethane, butane, hexane ordiethyl ether. Compounds which decompose at temperatures above roomtemperature with liberation of gases, e.g., nitrogen, such as azocompounds, azoisobutyric acid nitrile, may also act as blowing agents.Compressed air may act as a blowing agent. Other examples of blowingagents and details about the use of blowing agents are described inKunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 108 and 109, 453 to 455and 507 to 510.

The proportions of the components may be adjusted to a highly cellularsolid. When water is used, it reacts with the NCO group to produce CO₂and pores are produced in the producy by the evolved CO₂. In certaincases, the CO₂ is rapidly evolved and escapes before the producthardens, and a solid product can be produced, nearly completely free ofair cells. When a high silicate content, from 80% to 99% by weight, isdesirable, such as when the final product is required to have mainly theproperties of an inorganic silicate plastic, in particular,high-temperature resistance and complete flame resistance, an alkalimetal silicate may be added with copolymer or polyol or be reacted withthe polyisocyanate to produce a polyurethane prepolymer. In that case,the function of the polyisocyanate is that of a non-volatile hardenerwhose reaction product is a high-molecular-weight polymer which reducesthe brittleness of the product.

When an alkali catalyst or alkali metal silicate is used in theinvention, fine metal powders, e.g., powdered calcium, magnesium,aluminum or zinc, may also act as the blowing agents by bringing aboutthe evolution of hydrogen. Compressed air may be mixed in the componentsand may also be used to mix the components, then be used as the blowingagent. These metal powders also have a hardening and reinforcing effect.

The properties of the foams (cellular solid) obtained from any givenformulation, e.g., their density in the moist state, depends to someextent on the details of the mixing process, e.g., the form and speed ofthe stirrer and the form of the mixing chamber, and also the selectedtemperature at which foaming is started. The foams will usually expand 3to 12 times their original volume.

The polyurethane silicate plastics produced by the invention have manyuses. The reaction mixture, with or without a blowing agent, may bemixed in a mixing apparatus; then the reaction mixture may be sprayed bymeans of compressed air or by the airless spraying process ontosurfaces; subsequently, the mixture expands and hardens in the form of acellular solid which is useful for insulation, filling andmoisture-proofing coating. The foaming material may also be forced,poured or injection-molded into cold or heated molds, which may berelief molds or solid or hollow molds, optionally by centrifugalcasting, and left to harden at room temperature or at temperatures up to200° C., at ambient pressure or at elevated pressure. In certain cases,it may be necessary to heat the mixing or spraying apparatus to initiatefoaming; then, once foaming has started, the heat evolved by thereaction between components continues the foaming until the reaction iscomplete. A temperature between 40° C. and 150° C. may be required toinitiate foaming. The blowing agent is usually added to thepolyisocyanate.

Reinforcing elements may quite easily be incorporated into the reactionmixtures. The inorganic and/or organic reinforcing elements may be,e.g., fibers, metal wires, foams, fabrics, fleeces or skeletons. Thereinforcing elements may be mixed with the reaction mixtures, forexample, by the fibrous web impregnation or by processes in which thereaction mixtures and reinforcing fibers are together applied to themold, for example, by means of a spray apparatus. The shaped productsobtainable in this way may be used as building elements, e.g., in theform of sandwich elements, either as such or after they have beenlaminated with metal glass or plastics; if desired, these sandwichelements may be foamed. The products may be used as hollow bodies, e.g.,as containers for goods which may be required to be kept moist or cool,as filter materials or exchangers, as catalyst carriers or carriers ofother active substances, as decorative elements, furniture componentsand fillings or for cavities. They may be used in the field of modelbuilding and mold building, and the production of molds for metalcasting may also be considered.

Instead of blowing agents, finely divided inorganic or organic hollowparticles, e.g., hollow expanded beads of glass, plastics and straw, maybe used for producing cellular solid products. These products may beused as insulating materials, cavity fillings, packaging materials,building materials which have good solvent resistance and advantageousfire-resistant characteristics. They may also be used as lightweightbuilding bricks in the form of sandwiches, e.g., with metal-coveringlayers for house building and construction of motor vehicles andaircraft.

Organic or inorganic particles which are capable of foaming up or havealready been foamed may be incorporated in the fluid foaming reactionmixture, e.g., expanded clay, expanded glass, wood, cork, popcorn,hollow plastic beads such as beads of vinyl chloride polymers,polyethylene, styrene polymers, or foam particles of these polymers orother polymers, e.g., polysulphone, polyepoxide, polyurethane,poly(urethane silicate) copolymers, urea-formaldehyde,phenol-formaldehyde or polyamide polymers, or, alternatively, heaps ofthese particles may be permeated with foaming reaction mixtures toproduce insulation materials which have good fire-resistantcharacteristics.

The cellular solid products of the invention, in the aqueous or dry orimpregnated state, may subsequently be lacquered, metallized, coated,laminated, galvanized, vapor treated, bonded or blocked. The cellularsolid products may be sawed, drilled, planed, polished, or other workingprocesses may be used to produce shaped products. The shaped productswith or without a filler, may be further modified in their properties bysubsequent heat treatment, oxidation processes, hot pressing, sinteringprocesses or surface melting or other compacting processes.

The novel cellular solid products of the invention are also suitable foruse as constructional materials due to their toughness and stiffness,yet they are still elastic. They are resistant to tension andcompression and have a high dimensional stability to heat and high flameresistance. They have excellent sound-absorption capacity,heat-insulating capacity, fire resistance, and heat resistance whichmakes them useful for insulation. The cellular products of thisinvention may be foamed on the building site and, in many cases, used inplace of wood or hard fiber boards. Any hollow forms may be used forfoaming. The brittle foams may be crushed and used as a filler, as asoil conditioner, as a substrate for the propagation of seedlings,cuttings and plants or cut flowers.

The foamed or solid concrete produced by reacting the broken downlignin-cellulose silicate copolymer, polyol and polyisocyanate with awater-binding component may be used as surface coatings having goodadhesion and resistance-to-abrasion properties, as mortars, and formaking molded products, particularly in construction engineering andcivil engineering such as for building walls, igloos, boats and forroadbuilding, etc. These products are light-weight, thermal-insulatingmaterials with excellent mechanical properties and fire resistance. Theamount of water-binding component used varies greatly, depending on thetype of product desired, from 1% to 200% by weight, based on thecomponents. In certain cases, it is desireable to add sand and gravel inthe amount of 1 to 6 parts by weight to each part by weight of thehydraulic cement. The mixture may be poured in place, troweled on orsprayed onto the desired surface to produce a solid or cellular solidproduct.

Fillers in the form of powders, granules, wire, fibers, dumb-bell shapedparticles, crystallites, spirals, rods, beads, hollow beads, foamparticles, non-woven webs, pieces of woven or knitted fabrics, tapes andpieces of foil of solid inorganic or organic substances, e.g., dolomite,chalk, alumina, asbetstos, basic silicic acids, sand, talc, iron oxides,aluminum oxide and hydroxides, alkali metal silicates, zeolites, mixedsilicates, calcium silicate, calcium sulphates, alumino silicates,cements, basalt wool or powder, glass fibers, carbon fibers, graphite,carbon black, Al-, Fe-, Cri- and Ag-powders, molybdenum sulphide, steelwool, bronze or copper meshes, silicon powder, expanded clay particles,hollow glass beads, glass powder, lava and pumice particles, wood chips,woodmeal, cork, cotton straw, popcorn, coke or particles of filled orunfilled, foamed or unfoamed, stretched or unstretched organic polymersmay be added to the mixture of the Components a, b and c in manyapplications. Among the numerous organic polymers which may be used,e.g., as powders, granules foam particles, beads, hollow beads, foamable(but not-yet-foamed) particles, fibers, tapes, woven fabrics, orfleeces, the following may be mentioned as examples: polystyrene,polyethylene, polypropylene, polyacrylonitrile, polybutadiene,polyisoprene, polytetrafluoroethylene, aliphatic and aromaticpolyesters, melamine, urea, phenol resins, phenol silicate resins,polyacetal resins, polyepoxides, polyhydantoins, polyureas, polyethers,polyurethanes, polyimides, polyamides, polysulphones, polycarbonates andcopolymers thereof.

The composite materials, according to the invention, may be mixed withconsiderable quantities of fillers without losing their advantageousproperties, and, in particular, composite materials which consistpredominantly of organic constituents which are preferably filled withinorganic fillers; where silicate constituents predominant, it ispreferably filled with organic fillers. Fillers which are particularlypreferred are chalk, talc, dolomite, gypsum, clay, anyhydrite, glass,carbon and the conventional plastics and rubber waste.

In the production of surface coatings, bonds, putties or interlayers,particularly in the case of porous materials, it is preferred to usepolyisocyanates which have only a low isocyanate content, e.g., lessthan 5%, or prepolymers which are free from isocyanate groups. Themixtures obtained in this way have a long pot life and may be applied inthin layers which gradually harden in the course of time. The liberatedCO₂ acts as the curing agent. In a two-stage or multistage hardening inwhich, for example, an excess of water is used, there is a rapidevolution of CO₂ and the polyurethane silicon acid resinous product isconverted into a workable form which may be used as putties, coatingagents, grouting materials or mortar. This thermoplastic form may alsobe injection-molded, extruded or worked-up in a kneader.

In many cases, the polyurethane silicate resinous and foamed productsproduced by the invention are soluble in organic solvents and may beused as a tough coating agent for wood and metal. The mixtures of theinvention are also suitable for use as impregnating agents for finishingfibers. The mixtures may also be extruded through dies or slots andconverted into fibers and foils. These fibers and foils may be used forproducing synthetic incombustible paper or fleeces.

When broken down lignin-cellulose silicate copolymer and polyisocyanateare combined with expanded clay and an alkali metal silicate solution, avery good concrete is obtained which can, for example, be used as panelsin the construction field. In this case, the foam material (expandedclay) plays the part of the binding material.

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail by the specificexample which follows, it being understood that these preferredembodiments are illustrative of, but not limited to, procedures whichmay be used in the production of broken down lignin-cellulose silicatecopolymers. Parts and percentages are by weight unless otherwiseindicated.

EXAMPLE 1

About 2 parts by weight of fir sawdust, 1 part by weight of hydratedsilica and 1.5 parts by weight of sodium hydroxide flakes are mixed,then heated to 150° C. to 220° C. while agitating at ambient pressurefor 5 to 60 minutes or until the mixture softens and expands into abrown, thick liquid which solidifies on cooling, thereby producing abroken down sodium lignin-cellulose silicate product.

Water is added to the broken down sodium lignin-cellulose silicatepolymer to produce a 30% aqueous solution which is filtered to removeany unreacted cellulose then ethylene dichloride is slowly added to thesolution, in amount wherein the sodium atoms about equal the chlorideatoms, while vigorously agitating the mixture and heating the mixture tojust below the boiling temperature of ethylene dichloride whilevigorously agitating for about 30 minutes. The reaction is complete in30 minutes to 8 hours thereby producing a light brown broken downlignin-cellulose silicate copolymer which settles out. The water, saltand unreacted components are removed filtration. The reaction time isdecreased by utilizing elevated pressure and temperature.

EXAMPLE 2

About 2 parts by weight of small plant particles listed below, 1 part byweight of silica sol and 2 parts by weight of sodium hydroxide aremixed, then heated to 150° C. to 220° C. while agitating at ambientpressure, with care being taken to avoid burning the mixture, for 5 to60 minutes; the mixture begins to expand and a brown, thick liquid,broken down sodium cellulose polymer. The liquid solidifies on coolingand is ground into a powder. The powder is soluble in water, alcohols,polyhydric organic compounds and other solvents.

(a) oak sawdust

(b) fir sawdust

(c) cotton

(d) corn cobs

(e) cotton stalks

(f) ash sawdust

(g) seaweed

(h) bagasse

(i) paper

(j) oat straw

Water is added to the broken down sodium lignin-cellulose silicatepolymer produced from oak sawdust filtered to remove any unreactedsawdust, and a 50% aqueus solution of the broken down sodiumlignin-cellulose silicate polymer is produced; then propylene dichlorideis slowly added to the solution, in an amount wherein the chloride atomsare about equal to the sodium atoms, while vigorously agitating themixture while heating to just below the boiling temperature of propylenedichloride for about 30 minutes. The reaction is complete in 30 minutesto 8 hours thereby producing a light brown lignin-cellulose silicatecopolymer which precipitates out. The water, salt and unreactedcomponents are removed by filtration.

EXAMPLE 3

Methylene chloride is slowly added to an aqueous solution containing 40%broken down sodium lignin-cellulose silicate as produced in Example 2eand 2% sodium lignin sulfonate while agitating and heating the solutionto a temperature just below the boiling temperature of methylenechloride for 30 minutes. The reaction is complete in 30 minutes to 8hours thereby producing a broken down lignin-cellulose silicatecopolymer. The methylene chloride is added in an amount wherein thechloride atoms are about equal to the sodium atoms. Elevated pressuremay be used.

EXAMPLE 4

The broken down alkali lignin-cellulose silicate polymer produced inExample 2f is mixed with ethyl oxolate in an about equal amount whileagitating for about 30 minutes thereby producing a broken downlignin-cellulose silicate polymer. The copolymer is recovered byfiltration.

EXAMPLE 5

Propane-1,3-dihydrogen phosphate is slowly added to an aqueous solutioncontaining 30% by weight of a broken down alkali metal lignin-cellulosesilicate polymer as produced in Example 2h and 3% by weight of methylcellulose, in an amount wherein the phosphate radicals are aboutequivalent to the sodium radicals while agitating at a temperature justbelow the boiling temperature of the reactants for 30 minutes. Thereaction is complete in 30 minutes to 8 hours thereby producing a brokendown lignin-cellulose silicate copolymer.

EXAMPLE 6

About 3 parts by weight of a broken down alkali metal lignin-cellulosesilicate as produced in Example 2f are ground into a fine powder thenbis (2-chloroethyl)ether, in the amount wherein the chlorine atoms areabout equal to the sodium atoms in the mixture, is slowly added whileagitating at a temperature just below the boiling temperature ofbis(2-chloroethyl)ether for about 30 minutes. The reaction is completein 30 minutes to 8 hours thereby producing a broken downlignin-cellulose silicate copolymer.

EXAMPLE 7

An amount of para-dinitrobenzene, wherein the nitro and alkali metalradicals are about equal is slowly added to the broken down alkali metallignin-cellulose silicate produced in 2b while agitating at atemperature just below the boiling temperature of paradinitrobenzene forabout 30 minutes. The reaction is complete in 30 minutes to 8 hoursthereby producing a broken down lignin-cellulose silicate copolymer.

EXAMPLE 8

About 10 parts by weight of broken down alkali metal lignin-cellulosesilicate as produced in Example 2j are dissolved in ethanol thenbutan-1,4-di(hydrogen sulfate) is slowly added, in an amount wherein thehydrogen sulfate radicals are about equal to the sodium radicals whileagitating for about 30 minutes. The reaction is complete in 30 minutesto 8 hours, thereby producing a brown broken down lignin-cellulosesilicate copolymer.

Other disubstituted organic compounds may be used in place ofbutane-1,4-di(hydrogen sulfate) such as para dichlorobenzene;2,4-dinitrotoluene; chloroform; 1,3-dichloro-2-propanol;bis(2chloroethyl) formal; 1,3-dibromopropane; methylene chloride;1,4-dibromo-2-butene; 1,3-chloromethoxy 2,2-di-methyl propane;dichloroethyl carbonate; 2,4-dinitrobenzene sulfonic acid;p,p'-dichlorobenzyl and mixtures thereof.

EXAMPLE 9

About equal parts by weight of the broken down alkali metallignin-cellulose silicate as produced in Example 2b and sodiumpolysulfide (Na₂ S_(x) wherein x=4 to 5) are added to water to producean aqueous solution containing 40% solids then ethylene chloride, in anamount wherein the chlorine atoms are about equal to the sodium atoms,are slowly added, while agitating for about 30 minutes while keeping thetemperature just below the boiling point of the reactants. The reactionis complete in 30 minutes to 8 hours thereby producing a lightbrown-colored, somewhat elastic, poly(organic polysulfide broken downlignin-cellulose silicate) copolymer.

Other disubstituted organic compounds may be used in place of ethylenechloride such as para dichlorobenzene, 2,4-dinitrotoluene; tolylenediisocyanate; chloroform; 1,3-dichloro-2-propanol; bis(2 chloroethyl)formal; 1,3-dibromopropane; butane-1,4-di(hydrogen sulfate);dichloroethyl ether; methylene chloride; 1,4-dibromo-2-butene;1,3-chloromethoxy 2,2-di-methyl propane; dichloroethyl carbonate;2,4-dinitrobenzene sulfonic acid and p p'-dichlorobenzyl.

EXAMPLE 10

About 3 parts by weight of sulfur and 2 parts by weight of granularsodium silicate are mixed and then heated to just above the meltingtemperature of sulfur while agitating at ambient pressure for 10 to 30minutes, thereby producing an alkali metal-sulfur-silicate condensationproduct.

About 5 parts by weight of the alkali metal-sulfur-silicate condensationproduct and 10 parts by weight of the broken down sodiumlignin-cellulose silicate as produced in Example 2 are added to water toproduce an aqueous solution containing 50% solids thenbis(2-chloroethyl) ether, in an amount wherein the chloride atoms areabout equal to the sodium atoms, is slowly added while agitating andkeeping the temperature just below the boiling temperature of thereactants for about 30 minutes, the reaction is complete in 30 minutesto 8 hours, thereby producing a light brown in color somewhat elasticpoly (organic polysulfide silicate broken down lignin-cellulosesilicate) copolymer.

Any of the other previously described disubstituted organic compoundsmay be used in place of the bis(2-chloroethyl) ether in this example,such as ethylene dichloride, ethylene dibromide, propylene dichloride ordibromide, dihalides of unsaturated hydrocarbon gases derived frompressure-cracking processes; natural gas-cracking processes, polyhalidealkanes such as 1,1,2-trichloroethane; 1,2,4-trichlorobutane;trichloromesitylene; compounds containing disubstituted halogens, acidsulfates, nitrates, acid phosphates, bicarbonates, formates, acetates,propionates, laurate, oleate, stearate, oxalate, acid malonate, acidtartrate, acid citrate and mixtures thereof such as: A A'disubstitutedethyl ether, B B'disubstituted ethyl ether, disubstituted methyl ether,disubstituted ethoxy ethyl ether, disubstituted thio ethyl,disubstituted 1,3-methoxy 2,2-di-methyl propane, disubstituted dipropylformal, disubstituted para-diethoxy benzene, disubstituted dimethoxyethane, disubstituted diethyl carbonate, disubstituted glycol diacetate,p p'disubstituted dibenzyl ether, p p'disubstituted diphenyl ether,disubstituted diethyl sulphone, A A'disubstituted propyl ether,para-disubstituted benzene, disubstituted para-xylene, p,p'-disubstituted dibenzyl, disubstituted para hexyl propyl benzene,disubstituted 3-toyl propene-2, mixtures thereof.

EXAMPLE 11

About 10 parts by weight of the broken down sodium lignin-cellulosesilicate polymer as produced in 2b and 10 parts by weight ofpolyethylene glycol (mol. wt. 380 to 420) are mixed and heated until thepolymer goes into solution then ethylene chloride is slowly added in anamount wherein the chlorine atoms about equal the sodium atoms whileagitating at a temperature just below the boiling point of ethylenechloride for about 30 minutes thereby producing a broken down ethylenelignin-cellulose silicate copolymer.

About 10 parts by weight of TDI is added to the ethylenelignin-cellulose silicate copolymer in the polyethylene glycol andthoroughly mixed at ambient temperature. The mixture begins to expand ina few seconds and expands 8 to 12 times its original volume to produce arigid polyurethane silicate foam which is light brown in color, toughand somewhat flexible.

Other polyols and polyisocyanate may be used in this example in place ofpolyethylene glycol and TDI. The polyurethane foam may be produced inlarge slabs then cut into sheets of the desired thickness and use assound and thermal insulation in homes, buildings, aircraft andautomobiles.

EXAMPLE 12

Diethyl oxalate is slowly added in an amount when in 1 mol of thediethyl oxalate is added per 2 mols of the sodium hydroxide present inthe broken down sodium lignin-cellulose silicate polymer produced in 2bwhile agitating at a temperature just below the boiling point of thediethyl oxalate for about 30 minutes thereby produce brown granules abroken down organic lignin-cellulose silicate copolymer.

The polymer is then washed with water filtered to remove the salt, thendried. The dried polymer is then heated to 160° to 200° C. then forcedinto a mold under pressure to produce a useful object such as knobs,handles, art objects, etc., which are brown in color and are rigid andtough.

EXAMPLE 13

About 10 parts of the broken down organic lignin-cellulose silicatecopolymer as produced in Example 12 is mixed with 10 parts by weight ofpolyethylene glycol (mol. wt. 380-420) is mixed and the copolymer goesinto solution then 15 parts by weight of TDI are added and thoroughlymixed. About 1 part by weight of triethylamine is added and thoroughlymixed. The mixture begins to expand in a few seconds. The mixtureexpands 8 to 12 times its original volume thereby producing a rigid,cream colored polyurethane foam.

EXAMPLE 14

About 10 parts by weight of broken down alkali metal lignin-cellulosesilicate polymer as produced in Example 1 and 5 parts by weight of anaqueous solution containing 37% by weight of formaldehyde are mixed thenheated to below the boiling point of the reactants while agitating for10 to 120 minutes thereby producing an aldehyde-broken down alkali metallignin-cellulose silicate polymer; then 1 propane-1,3-dihydrogen sulfateis added to the aqueous solution of aldehyde-broken down alkali metallignin-cellulose silicate polymer in an amount wherein the hydrogensulfate radicals are about equal to the alkali metal radicals, whileagitating at ambient temperature and pressure for about 30 minutes. Thereaction is complete in 30 minutes to 8 hours thereby producing analdehyde broken down lignin-cellulose silicate propionate copolymer.

Other aldehydes may be used in place of formaldehyde such asacetaldehyde, propionic aldehyde, furfural, crotonaldehyde, acrolein,genzaldehyde, butyl aldehyde, pentanals, hexanals, heptanals, octanalsand mixtures thereof.

Other substituted organic compound listed in the specification may beused in place of propane dihydrogen sulfate.

EXAMPLE 15

The dried powdered broken down organic lignin-cellulose silicatecopolymer as produced in Example 12 is mixed with about equal parts byweight of "MDI" and 1% by weight of trimethylamine. The mixture expandsin a few seconds to produce a rigid polyurethane foam.

EXAMPLE 16

About 2 parts by weight of the broken down lignin-cellulose silicatecopolymer as produced in Example 1 and 2 parts by weight of anisocyanate-terminated polyurethane prepolymer listed below and 0.2 partsby weight of water containing 1% by weight of triethyleneamine and 30%by weight of sodium silicate are mixed and in a few minutes a solidpolyurethane silicate resinous product is produced. This resinousproduct may be used as a cavity filler.

    __________________________________________________________________________    Example                                                                            isocyanate-terminated polyurethane prepolymer                            __________________________________________________________________________    a    polyphenyl-polymethane-isocyanate with polyethylene oxide                     monohydric alcohol (mol. wt. 1100), initiated on trimethylol                  propane to produce a prepolymer with a NCO content of about                   18%.                                                                     b    TDI with polyethylene (mol. wt. 1000) to produce a prepolymer                 with a NCO content of about 24%.                                         c    residue of tolylene diisocyanate distillation with about 20%                  by weight of NCO with polyethylene glycol (mol. wt. 1500) to                  produce a prepolymer with a NCO content of about 10%.                    d    tolylene diisocyanate with castor oil to produce a prepolymer                 with a NCO content of about 15%.                                         e    tolylene diisocyanate with a liquid hydroxyl-terminated poly-                 butadiene (mol. wt. 500) to produce a prepolymer with a NCO                   content of about 7%.                                                     f    toluene diisocyanate with a hydroxyl-group-containing                         polysulfide polymer to produce a prepolymer with a NCO                        content of about 12%.                                                    g    methylene bis-phenyl diisocyanate with a liquid poly-                         epichlorohydrin to produce a prepolymer of about 16%.                    h    tolylene diisocyanate with a polyester (4 mols. of                            gycerol, 2.5 mols of adipic acid and 0.5 mol of phthalic                      anhydride) to produce a prepolymer with a NCO content of                      about 20%.                                                               __________________________________________________________________________

EXAMPLE 17

About 10 parts by weight of the aldehyde broken down lignin-cellulosesilicate propionate copolymer, 10 parts by weight of a sucrose aminepolymer (POLY G 71-356 produced by Olin Chemical), 15 parts by weight ofMDI and 10 parts by weight of sodium metal silicate pentahydrate aremixed at 30°-40° C. The mixture begins to expand in 15-45 seconds andexpands 8 to 12 times its original volume to produce a rigid toughpolyurethane silicate foam. The foam is flame resistant and may be usedin construction of doors, panels and used as thermal and soundinsulation. It may be cut into the desired width and thickness. Otheralkali metal silicates may be used in place of sodium silicate.

EXAMPLE 18

About 10 parts by weight of the dried broken down lignin-cellulosesilicate copolymer as produced in Example 1, 10 parts by weight ofpolypropylene glycol (mol. wt. 1200) 0.5 parts by weight of "DABCOR-8020" (triethylenediamine and dimethylethanolamine), produced by AirProducts, 15 parts by weight of MDI ("PAPA 27" produced by Upjohn), 30parts by weight of Portland Cement and 30 parts by weight of plaster'ssand are mixed thoroughly. The mixture is then poured into 4"×6"×16"concrete block molds in the amount of 1/2"-3/4" in depth. In a fewseconds to 1 minute the mixture begins to expand and fills the molds.The mixture hardens within 5 minutes and is taken from the mold andplaced in water for about 2 minutes. The excess cement is cured with thewater thereby producing polyurethane silicate concrete blocks. Theseblocks may be used for building walls which have excellent insulationand flame resistant properties.

Although specific materials and conditions were set forth in the aboveexamples, these were merely illustrative of preferred embodiments of myinvention. Various other compositions, such as the typical materialslisted above may be used, where suitable. The reactive mixtures andproducts of my invention may have other agents added thereto to enhanceor otherwise modify the reaction and products.

Other modifications of my invention will occur to those skilled in theart upon reading my disclosure. These are intended to be included withinthe scope of my invention, as defined in the appended Claims.

I claim:
 1. The process for the production of broken downlignin-cellulose silicate copolymer by mixing and reacting the followingcomponents:Component (a) chemically broken down alkali metallignin-cellulose silicate polymer. Component (b) an organic compoundhaving the graphical skeleton carbon structure of where

    X--C--C--X

    --C--C--

represents two adjacent carbon atoms, or

    X--C--R--CX

where X and X represent the substituents which splet off during thereaction. The R between the pair of reactive carbon atoms is selectedfrom the following groups: saturated straight chain carbon atoms,unsaturated carbon atoms, ether linkages and aromatic structures. The Xand X substituents can be halogen, acid sulfate, nitrate, acidphosphate, bicarbonate, formate, acetate, propionate, laurate, oleate,stearate, oxalate, acid malonate, acid tartrate and acid citrate.
 2. Theprocess of claim 1 wherein the substituted organic compound is selectedfrom the group consisting of A A' disubstituted ethyl ether; B B'disubstituted ethyl ether; disubstituted methyl ether; disubstitutedethoxy ethyl ether; disubstituted thio ethyl ether; disubstituted 1,3methoxy 2,2 dimethyl propane; disubstituted dipropyle formal,disubstituted diethyl formal; disubstituted para diethoxy benzene;disubstituted dimethoxy ethane; disubstituted diethyl carbonate;disubstituted glycol diacetate; p p' disubstituted diphenyl ether;disubstituted dibenzyl ether; disubstituted diethyl sulphone; A A'disubstituted propyl ether; para disubstituted benzene; disubstitutedpara xylene; p p' disubstituted dibenzyl; disubstituted para hexylpropyl benzen; disubstituted 3-toyl propene-2; ethylene dichloride;ethylene dibromide; propylene dichloride; propylene dibromide; dihalidesof unsaturated hydrocarbon gases derived from pressure-crackingprocesses and material gas-cracking processes; 1,1,2 trichloroethane;1,2,4-trichlorobutane; and mixtures thereof.
 3. The process of claim 2wherein the substituted organic compound contains at least twosubstituents, selected from the group consisting of acid sulfate,nitrate, acid phosphate, bicarbonate, formate acetate, propionate,laurate, oleate, stearate, oxalate, acid malonate, acid tartrate, acidcitrate, halogens, and mixtures thereof.
 4. The process of claim 1wherein an emulsifying or dispersing agent selected from the groupconsisting of lignin sulfonates alkyl aryl sulfonates, aryl alkylsulfonates, sorbitan monolaurates, alkyl aryl sulfates, methylcellulose, sulfonated petroleum fractions, polymerized alkyl arylsulfonates, polymerized aryl alkyl sulfonates, soybean lecithin andmixtures thereof in an aqueous solution is added to the unreactedmixture.
 5. The process of claim 1 wherein lignin sulfonate in anaqueous solution is added to the unreacted mixture as an emulsifying ordispersing agent.
 6. The process of claim 1 wherein the substitutedorganic compound is ethylene dichloride.
 7. The product produced by theprocess of claim
 1. 8. The process of claim 1 wherein an additional stepis taken wherein a water soluble polysulfide in an aqueous solution isadded with the broken down alkali metal lignin-cellulose silicatepolymer, thereby producing a polysulfide-broken down lignin-cellulosesilicate condensation product.
 9. The product produced by the process ofclaim
 8. 10. The process according to claim 8 wherein the water solublepolysulfide is selected from the group consisting of alkali metalpolysulfide, alkaline earth metal polysulfide, ammonium polysulfide,polysulfides of ethanolamine, and mixtures thereof and added in theratio of 1 to 20 parts by weight of the water soluble polysulfide to 10parts by weight of the broken down alkali metal lignin-cellulosesilicate.
 11. The process of claim 1 wherein an additional step is takenwherein a water soluble alkali-sulfur-silicate condensation product isadded in an aqueous solution up to an amount equal to the broken downalkali metal lignin-cellulose silicate polymer, with the broken downalkali metal lignin-cellulose silicate polymer, thereby producing apolysulfide-silicate-broken-down lignin-cellulose silicate condensationproduct.
 12. The product produced by the process of claim
 11. 13. Theprocess of claim 11 wherein the water soluble alkali-sulfur-silicatecondensation product is produced by mixing 2 parts by weight of analkali metal hydroxide selected from the group consisting of sodiumhydroxide and potassium hydroxide, 1 to 4 parts by weight of sulfur and1 to 2 parts by weight of an oxidated silicon compound selected from thegroup consisting of silica, alkali metal silicate, alkaline earth metalsilicates, natural oxidated silicon compounds containing free silicicacid and/or oxide groups and mixtures thereof, then heating the mixtureto just above the melting temperature of sulfur while agitating for 10to 30 minutes thereby producing an alkali-sulfur-silicate condensationproduct.
 14. The process of claim 1 wherein the broken down alkali metallignin-cellulose silicate polymer is first added to a solvent selectedfrom the group consisting of water, methanol, ethanol, isopropylalcohol, ethylene glycol, propylene glycol, glycerol, furfuryl alcohol,polyester polymer with 2 or more hydroxyl groups, sucrose amine polymerwith 2 or more hydroxyl groups, polyether polymers with 2 or morehydroxyl groups and mixtures thereof.
 15. The process of claim 1 whereinthe broken down alkali metal lignin-cellulose silicate polymer is firstreacted with an aldehyde selected from the group consisting offormaldehyde, acetaldehyde, propionic aldehyde, furfural,crotonaldehyde, acrolein, butyl aldehyde, paraformaldehyde, pentanals,hexanals, heptanals and mixtures thereof in the ratio of 1 to 5 parts byweight of the broken down alkali metal lignin-cellulose silicatepolymer.
 16. The product produced by the process of claim 15.